This invention relates to the polymers formed by the reaction of amine-containing and/or hydroxy-containing synthetic polymers with the halohydrin glycoside of monosaccharides or oligosaccharides.
Ethylenically unsaturated mono- and disaccharide glycoside derivatives as well as homo- and copolymers derived therefrom have been prepared. See, for example, U.S. Pat. No. 3,356,652 issued on Dec. 5, 1967 to D. Ray-Chaudhuri which describes the preparation of a glycoside containing an ethylenically unsaturated side-chain linked to the number 1 carbon of a 2,3,4,6-tetra-O-acetylglucose molecule. The homo- and copolymers prepared from the acetylated glycosidic monomers are soluble in organic solvents. They are prepared by reacting a tetraacetylglycosyl halide with a monohydroxy or monocarboxy ethylenically unsaturated monomer. Upon deacetylation, the homo- and copolymers having a mole fraction of at least about 20% of the glucoside derivatives become readily water soluble with a greater hydrophilic character than other commonly available synthetic water soluble polymers. The polymers contain monosaccharide side chains represented by the formula ##STR2## where R' represents a residue of a monosaccharide which is bonded at its 1-position and Y' is the residue after the polymerization of one of the following groups: ##STR3## with Z being hydrogen or methyl and Q being a C.sub.1 -C.sub.4 oxyalkyl group. The polymers are described as having broad utility in the adhesive, textile, and paper industries.
Similarly, U.S. Pat. No. 4,328,337 issued May 4, 1982 to T. Kawasaki et al. describes the preparation of polymers having repeating mono- or disaccharide side chains represented by the formula ##STR4## where R represents a hydrogen atom or a methyl group, R.sup.1 represents a residue of a saccharide selected from the group consisting of glucose, fructose, maltose, mannose, lactose, and cellobiose, which is acyl-bonded at its 1-position, and n is 10-1000. They are prepared by homopolymerizing (meth)acryloyl mono- or disaccharide glycosides, e.g., ##STR5## where R.sup.2 represents an acetylated glucose residue acryl-bonded at its 1-position, and then de-acetylating the resulting polymer using an agent such as sodium methylate and ammonia at lower than room temperature. They may also be synthesized by bonding the saccharide chains to the main chain of the polymer, e.g., by reacting a polymer of acrylic or methacrylic acid with the compound obtained by orthoesterifying the hydroxyl group of the terminal reducing part of the acetylated saccharide and then de-acetylating the final polymer. The polymers are wter soluble with excellent bio-adaptability and membrane-forming properties. When cross-linked, the homopolymers have a high water-retaining property which is useful for many medical treatments.
In the prior art, the modifications of polyamines (e.g., proteins) with carbohydrates were made via reductive amination (e.g., using sodium cyanoborohydride), amide formation (e.g., using 2-imino-2-methoxyethylthioglycoside), or diazo coupling. The first two methods require the presence of primary or secondary amines. The reductive amination reaction results in an acyclic poly-alcohol attached to the nitrogen via a carbon-nitrogen bond. The thioglycoside, used in the amide formation or diazo coupling, is relatively stable to acid hydrolysis, i.e., cleavage of the glycoside bond. The reaction of reducing sugars with .alpha.-amino lysyl residues of casein in the presence of sodium cyanoborohydride is described in "Preparation and Nutritional Properties of Caseins Covalently Modified with Sugar. Reductive Alkylation of Lysines with Glucose, Fructose, or Lactose" by H. S. Lee et al., J. Agric. Food Chem. 27, #5, p. 1094 (1979). The covalent attachment of glycosides to proteins by amidination, diazo coupling reaction, and amide formation is described in "Attachment of Thioglycosides to Proteins: Enhancement of Liver Membrane Binding", by M. J. Krantz et al., Biochemistry 15, #18, p. 3963 (1976).
In U.S. Pat. No.3,931,148 issued on January 6, 1976 to W. Langdon, novel neutral and cationic glycosidic surfactants are prepared by reacting a 2-hydroxy-3-chloropropyl glycoside of a mono- or polysaccharide with an alkyl amine which contains at least one hydrophobic C.sub.8 -C.sub.18 alkyl group. The alkyl amines are described as having 8-30 carbon atoms which may be primary, secondary, tertiary, aliphatic, saturated or unsaturated, alicyclic aralkyl. The glycosides are described as being useful in areas requiring surfactants exhibiting biodegradability, alkali solubility and stability.
It is the object of this invention to produce a novel class of monosaccharide and oligosaccharide derivatives of synthetic polymers and proteins.